School of Pharmacy, Changzhou University, Changzhou, 213164, Jiangsu, China.
Department of Analytical Chemistry, China Pharmaceutical University, Nanjing, 210009, Jiangsu, China.
Mikrochim Acta. 2024 Sep 9;191(10):584. doi: 10.1007/s00604-024-06663-z.
Innovative chiral capillary silica monoliths (CSMs) were developed based on DNA nanoflowers (DNFs). Baseline separation of enantiomers such as atenolol, tyrosine, histidine, and nefopam was achieved by using DNF-modified CSMs, and the obtained resolution value was higher than 1.78. To further explore the effect of DNFs on enantioseparation, different types of chiral columns including DNA strand containing the complementary sequence of the template (DCT)-modified CSMs, DNF-modified CSMs, and DNF-modified CSMs were prepared as well. It was observed that DNF-modified CSMs displayed better chiral separation ability compared with DCT-based columns. The intra-day and inter-day repeatability of model analytes' retention time and resolution kept desirable relative standard deviation values of less than 8.28%. DNF/DNF-modified CSMs were able to achieve baseline separation of atenolol, propranolol, 2'-deoxyadenosine, and nefopam enantiomers. Molecular docking simulations were performed to investigate enantioselectivity mechanisms of DNA sequences for enantiomers. To indicate the successful construction of DNFs and DNF-modified CSMs, various charaterization approaches including scanning electron microscopy, agarose gel electrophoresis, dynamic light scattering analysis, electroosmotic flow, and Fourier-transform infrared spectroscopy were utilized. Moreover, the enantioseparation performance of DNF-modified CSMs was characterized in terms of sample volume, applied voltage, and buffer concentration. This work paves the way to applying DNF-based capillary electrochromatography microsystems for chiral separation.
基于 DNA 纳米花（DNF）开发了创新的手性毛细管硅胶整体柱（CSM）。使用 DNF 修饰的 CSM 实现了对如阿替洛尔、酪氨酸、组氨酸和奈福泮等对映异构体的基线分离，并且获得的分辨率值高于 1.78。为了进一步探索 DNF 对映体分离的影响，还制备了包含模板互补序列的 DNA 链（DCT）修饰的 CSM、DNF 修饰的 CSM 和 DNF 修饰的 CSM 等不同类型的手性柱。观察到与基于 DCT 的柱相比，DNF 修饰的 CSM 显示出更好的手性分离能力。模型分析物保留时间和分辨率的日内和日间重复性保持了小于 8.28%的理想相对标准偏差值。DNF/DNF 修饰的 CSM 能够实现阿替洛尔、普萘洛尔、2'-脱氧腺苷和奈福泮对映异构体的基线分离。进行了分子对接模拟以研究 DNA 序列对映异构体的手性选择性机制。为了表明 DNF 和 DNF 修饰的 CSM 的成功构建，利用了各种特征化方法，包括扫描电子显微镜、琼脂糖凝胶电泳、动态光散射分析、电动流动和傅里叶变换红外光谱。此外，还根据样品体积、施加电压和缓冲液浓度来表征 DNF 修饰的 CSM 的对映体分离性能。这项工作为基于 DNF 的毛细管电色谱微系统用于手性分离铺平了道路。
